Incorporation of a (Cyclopentadienyl)molybdenum Oxo Complex in MCM‐41 and Its Use as a Catalyst for Olefin Epoxidation
作者:Marta Abrantes、Sandra Gago、Anabela A. Valente、Martyn Pillinger、Isabel S. Gonçalves、Teresa M. Santos、João Rocha、Carlos C. Romão
DOI:10.1002/ejic.200400386
日期:2004.12
tethered tricarbonyl complex using tert-butyl hydroperoxide (TBHP). The oxidised material is an active catalyst for the liquid phase epoxidation of cyclooctene with TBHP as the oxygen source. Similar catalytic results were obtained using the tethered tricarbonyl complex directly as a pre-catalyst since fast oxidative decarbonylation occurs under the reaction conditions used. For both systems, the desired
三羰基配合物 [(η5-C5H4-COOMe)Mo(CO)3Cl] 由(甲氧基羰基)环戊二烯化钠 (C5H4-CO2Me)Na 与 (Bu4N)[Mo(CO)5I] 反应制备。用3-(三乙氧基甲硅烷基)丙胺加热酯得到酰胺衍生物[η5-C5H4-CONH-C3H6Si(OEt)3]Mo(CO)3Cl}。通过在二氯甲烷中进行接枝反应,将官能化的三羰基复合物固定在负载量为 13 wt.-% Mo (1.4 mmol·g-1) 的有序介孔二氧化硅 MCM-41 中。粉末 X 射线衍射和氮吸附-解吸分析表明,尽管表面积、孔体积和孔径显着减小,但在接枝过程中载体的结构完整性得以保持,并且通道仍然可接近。偶联反应的成功由 29Si 和 13C (CP) MAS NMR 光谱证实。[(η5-C5H4R)MoO2Cl] 型负载型二氧合配合物随后通过使用叔丁基过氧化氢 (TBHP) 对束缚的三羰基配合物进行